5-carboxy-2-thiazolyl dithiocarbamates



United States Patent -CARBOXY-2-THIAZOLYL DITHIOCARBAMATES John J. DAmico, Charleston, W. Va., assignor to Monsanto Chemical Company, St. Louis, Mo., a corporation of Delaware No Drawing. Application May 3, 1954, Serial No. 427,354

Claims; (Cl. 260302) This invention relates to new compositions of matter and more particularly is directed to compounds containing the structure where R and R are hydrogen or hydrocarbon radicals and R" is an amino group in which the nitrogen is attached to the group and the remaining valen'ces of the nitrogen are satisfied by alkyl, aralkyl or alicyclic radicals or the nitrogen is part of a closed ring heterocyclic structure. Suitable amino groups are dimethylamino, diethylamino, di-isopropylamino, dipropylamino, dibutylamino, diamylamino, methyl cyclohexylamino, methyl tetrahydrofurfurylamino, dibenzylamino, di-B-phenethylamino, morpholinyl, piperidyl and a-methylpipen'dyl. In general it is preferred that R and R be short chain alkyl radicals such as methyl, ethyl, propyl and butyl.

The following specific examples are to be understood as illustrative of the invention but in nowise limitative of the scope thereof.

EXAMPLE 1 An aqueous solution containing 203.3 grams (1.0 mole) of 5-carbethoxy-4-methyl-2-thiazolethiol [Levi, Gazz. Chem. Ital. 61, p. 723 (1931)] and 160 grams (1.0 mole) of 25% sodium hydroxide in 2000 ml. of water was prepared and to this solution was added 151.7 grams (1.0 mole) of N,N-diethylthiocarbamyl chloride over a period of minutes. The mixture was stirred at 25-30 C. for two hours longer. The product was filtered ofi, washed with water until free from chloride, and air dried at room temperature. The- 5-carboethoxy-4-methyl-2- thiazolyl diethldithiocarbamate, M. P. 64-68? C., was obtained in 88.5% yield. After recrystallization from dilute ethyl alcohol the product melted at7576 C. Analysis gave 8.91% nitrogen and 30.60% sulfur as compared to 8.80% nitrogen and 30.20% sulfur calculated for C1zH1aN2O2S3- EXAMPLE 2 To a stirred solution containing 46.8 grams (0.244 mole) of S-carbomethoxy-4-methyl-2-thiazolethiol, 9.8 (0.244 mole) of sodium hydroxide and 388 ml. of water was added 37 grams (0.244 mole) of N,N-diethylthiocarbamyl chloride over a period of 15 minutes. The reaction mixture was stirred at 2530 C. for one hour longer. The solid was removed by filtration, washed with water until free of chloride and air dried at room temperature. The 5 carbomethoxy-4-methyl-2-thiazolyl diethyldithiocarbamate was obtained in 75.5% yield, M. P. 6466 C.

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2: After recrystallization from dilute methyl alcohol, it melted at 78-79 C. Analysis gave 9.47% nitrogen and 31.97% sulfur as compared to 9.20% nitrogen and 31.59% sulfur calculated for C11H1sN2O2S3.

EXAMPLE 3 To a stirred solution containing 231.4 grams 1.0 mole) of S-carbobutoxy-4-methyl-Z th-iazolethiol, and 160: grams (1.0 mole) of 25% sodium hydroxide in 2000 ml. of water was added 151.7 grams (1.0 mole) of N,N-d iethyltliiocarbamyl chloride over a period of 15 minutes. The reaction mixture was stirred for an additional twohours and then extracted with 900 ml. of ethyl ether. The ether solution was washed with water until the washings'were neutral to litmus, dried over sodium sulfate and the ether removed in vacuo. The 5-carbobutoxy-4-methyl-2-thiazolyl diethyldithiocarbarnate was a dark amber colored oil obtained in 78.3% yield. Analysis gave 830% nitrogen and 27.79% sulfur as compared to-8.08% nitrogen and 27.76% sulfur calculated for C14H22N2O2S3.

The new compounds are particularly useful as accelerators for Butyl rubber. The following compositions were prepared. p-Quinone dioxime is a well known accelerator and vulcanizing agent especially recommended for this polymer.

The compositions were cured by heating in a press for different periods of time at 330 F. The physical properties exhibited by the stocks at maximum cure were as follows:

Table I Modulus of Elasticity 2 3: in lbs.[in. at Tensile at Ultimate Stock Time Elonganons Break in igg in lbs/in. Perceht Mins A 30 1, 590 210 B 15 575 140 1, 550 635 C 30 575 1, 145 1, 650 600 As a further embodiment of the invention, stocks were compounded comprising Parts by weight Stock D E Butyl rubber 100 Carbon black 54 54 Zinc oxlde 5 5 Stearle acid. 1 1 65 Sulfur 1. 5 1. 5

p-Quinone Dioxime 6 Pba04 Mercaptobenzothiazole 0. 5 5-Carbobutoxy-4-methyl-2-thiazolyl d hyldith ocarbamate 1. 0

The compounded stocks were cured in the usual manner by heating in a press for different periods of time at C. The physical properties of the cured rubber products are set forth below:

It is intended to cover all changes and modifications of the examples of the invention herein chosen for purposes of disclosure which do not constitute departures from the spirit and scope of the invention.

What is claimed is:

1. A compound of the structure where R and R are selected from a group consisting of hydrogen and hydrocarbon radicals containing less than 5 carbon atoms and R" represents a secondary amino group containing less than 17 carbon atoms having the nitrogen attached to the C=S group.

2. A compound of the structure Where R and R represent alkyl radicals containing less than 5 carbon atoms and R" represents a dialkylamino radical containing less than 6 carbon atoms in each alkyl group.

3. A compound of the structure 0H3? CCOOR where R is an alkyl radical containing less than 5 carbon atoms.

4. A compound of the structure CHaC-(lJ C 0 OR 5 carbon atoms and R" represents a dialkylamino radical containing less than 6 carbon atoms in each alkyl group.

5. A compound of the structure 0113c ooooom 6. A compound of the structure CHaC|3---OO O O C2H5 7. A compound of the structure GHZO 0000mm S-CN(C:H5)z

8. The process which comprises condensing a S-carbalkoxy 4-alkyl-2-thiazolethiol of the structure R-C-N C-SH R'O-C-C-S with a thiocarbamyl halide, hlg

s h1 ilR" where R and R are selected from a group consisting of hydrogen and hydrocarbon radicals containing less than 5 carbon atoms, hlg represents halogen and R represents a secondary amino group containing less than 17 carbon atoms.

9. The process which comprises condensing a S-carbalkoxy 4-a1ky1-2-thiaz'olethiol of the structure R-C-N C-SH with N,N diethylthiocarbamyl chloride, where R and R are selected from a group consisting of hydrogen and hydrocarbon radicals containing less than 5 carbon atoms.

10. The process which comprises condensing a compound of the structure where R is an alkyl group of less than five carbon atoms with N,N-diethylthiocarbamyl chloride in aqueous alkaline medium.

References Cited in the file of this patent UNITED STATES PATENTS 2,186,421 Mathes Jan. 9, 1940 

1. A COMPOUND OF THE STRUCTURE 